EP0375990A2 - Process for the preparation of 1-amino-2-bromo-4-hydroxy-anthraquinone - Google Patents
Process for the preparation of 1-amino-2-bromo-4-hydroxy-anthraquinone Download PDFInfo
- Publication number
- EP0375990A2 EP0375990A2 EP89122183A EP89122183A EP0375990A2 EP 0375990 A2 EP0375990 A2 EP 0375990A2 EP 89122183 A EP89122183 A EP 89122183A EP 89122183 A EP89122183 A EP 89122183A EP 0375990 A2 EP0375990 A2 EP 0375990A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- amino
- anthraquinone
- bromo
- preparation
- hydroxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- KRNKIBUEHGMSIW-UHFFFAOYSA-N NC(C(CC1O)Br)C(C(C2=C3CCCC2)=O)=C1C3=O Chemical compound NC(C(CC1O)Br)C(C(C2=C3CCCC2)=O)=C1C3=O KRNKIBUEHGMSIW-UHFFFAOYSA-N 0.000 description 1
- VIJXURDPFPNEAV-UHFFFAOYSA-N NC(CCC1O)C(C(C2=C3C=CCC2)=O)=C1C3=O Chemical compound NC(CCC1O)C(C(C2=C3C=CCC2)=O)=C1C3=O VIJXURDPFPNEAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/24—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings
- C07C225/26—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings
- C07C225/32—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones the carbon skeleton containing carbon atoms of quinone rings having amino groups bound to carbon atoms of quinone rings or of condensed ring systems containing quinone rings of condensed quinone ring systems formed by at least three rings
- C07C225/34—Amino anthraquinones
- C07C225/36—Amino anthraquinones the carbon skeleton being further substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/503—Amino-hydroxy-anthraquinones; Ethers and esters thereof unsubstituted amino-hydroxy anthraquinone
Definitions
- the present invention relates to a new process for the preparation of 1-amino-2-bromo-4-hydroxyanthraquinone (I) by bromination of 1-amino-4-hydroxy-anthraquinone (II)
- DE-A 27 13 575 describes the preparation of (I) starting from 1-amino-anthraquinone, the starting compound first being converted into the 2,4-dibromo-anthraquinone in a sulfuric acid medium using bromine, which is then hydrolyzed with boric acid becomes.
- JP-A 042 631 relates to the halogenation of the mineral acid salts of (II) in inert organic solvents.
- this process is less selective with respect to monobromination and has been found to provide (I) with lower purity and only in 70-80% yields.
- 1-Amino-4-hydroxyanthraquinone (II) is known and can be obtained by known methods, e.g. by reacting 1,4-diaminoanthraquinone with manganese dioxide in sulfuric acid. For most purposes it is sufficient to use (II) in technical quality (about 95% by weight purity).
- the starting compound (II) is suspended in the inert organic liquid.
- suitable inert aprotic organic liquids are those compounds which themselves react only in insignificant amounts under the reaction conditions, including, preferably, monoaromatics substituted with electron-withdrawing groups, such as, for example, nitrobenzene, o-dichlorobenzene, trichlorobenzene or methyl benzoate.
- the amount of inert organic liquid is generally 4 to 12, preferably 6 to 9 kg per kg (II).
- Phosphorus tribromide, oxybromide or pentabromide or, above all, elemental bromine are used as brominating agents. These compounds are generally used in stoichiometric amounts, but it may also be advisable to use the brominating agent in an excess of 20 eq.%. A larger excess is less advisable with regard to working up the reaction mixture.
- reaction is carried out at 100 to 180, preferably at 120 to 140 ° C.
- the procedure is generally such that a suspension of II in the organic phase is initially introduced and the brominating agent is added at the reaction temperature. If necessary, the temperature can be increased as the reaction progresses.
- reaction is expediently carried out under normal pressure, but it is also possible to work in a closed system under autogenous pressure.
- the implementation can also be carried out continuously using the usual techniques, e.g. in a cascade of stirred tanks.
- reaction mixture is expediently cooled to about 25 ° C., after which the product is worked up in the customary manner, for example by it precipitates from the organic solution with methanol.
- the precipitated solid is filtered off and washed with methanol and water. It usually contains 90 to 98 wt.% (I).
- the purity can be determined chromatographically-photometrically using the usual techniques.
- 1-amino-2-bromo-4-hydroxy-anthraquinone (II) is an important intermediate in the production of anthraquinone solids such as e.g. Disperse Red 60 and Disperse Red 91.
- reaction mixture was then heated to 130 to 140 ° C. and held at this temperature for 3 hours.
- the mixture was then cooled to 25 ° C. and 250 g of methanol were added.
- the precipitated reaction product was filtered off, washed first with 250 g of methanol, then with water and dried.
Abstract
Description
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von 1-Amino-2-brom-4-hydroxy-anthrachinon (I)
In der DE-A 27 13 575 wird die Herstellung von (I) ausgehend von 1-Amino-anthrachinon beschrieben, wobei man zunächst die Ausgangsverbindung in schwefelsaurem Medium mit Brom in das 2,4-Dibrom-anthrachinon überführt, welches dann mit Borsäure hydrolysiert wird.DE-A 27 13 575 describes the preparation of (I) starting from 1-amino-anthraquinone, the starting compound first being converted into the 2,4-dibromo-anthraquinone in a sulfuric acid medium using bromine, which is then hydrolyzed with boric acid becomes.
Nach der Lehre de GB-A 1 239 778 wird die Halogenierung von Anthrachinonderivaten in Gegenwart von Mischungen aus einwertigen Alkoholen und inerten organischen Flüssigkeiten vorgenommen. Eigene Versuche haben jedoch gezeigt, daß die Bromierung unter diesen Bedingungen nur als Nebenreaktion abläuft.According to the teaching of GB-A 1 239 778, the halogenation of anthraquinone derivatives is carried out in the presence of mixtures of monohydric alcohols and inert organic liquids. However, our own experiments have shown that the bromination only takes place as a side reaction under these conditions.
Die JP-A 042 631 betrifft die Halogenierung der mineralsauren Salze von (II) in inerten organischen Lösungsmitteln. Dieses Verfahren ist jedoch weniger selektiv bezüglich der Monobromierung und liefert, wie festgestellt wurde, (I) mit geringerer Reinheit und nur in Ausbeuten von 70 bis 80 %.JP-A 042 631 relates to the halogenation of the mineral acid salts of (II) in inert organic solvents. However, this process is less selective with respect to monobromination and has been found to provide (I) with lower purity and only in 70-80% yields.
Da die bisher bekannten Verfahren in Bezug auf die Reinheit und die Ausbeuten unbefriedigend oder verfahrenstechnisch aufwendig sind, lag der Erfindung die Aufgabe zugrunde, diesen Mängeln abzuhelfen.Since the previously known methods are unsatisfactory in terms of purity and yields or are technically complex, the object of the invention was to remedy these deficiencies.
Demgemäß wurde ein neues Verfahren zur Herstellung von 1-Amino-2-brom-4-hydroxy-anthrachinon (I) durch Bromierung von 1-Amino-4-hydroxy-anthrachinon (II) gefunden, welches dadurch gekennzeichnet ist, daß man die Bromierung in einer inerten aprotischen organischen Flüssigkeit durchführt.Accordingly, a new process for the preparation of 1-amino-2-bromo-4-hydroxyanthraquinone (I) by bromination of 1-amino-4-hydroxyanthraquinone (II) has been found, which is characterized in that the bromination in an inert aprotic organic liquid.
1-Amino-4-hydroxy-anthrachinon (II) ist bekannt und nach bekannten Verfahren erhältlich, z.B. durch Umsetzung von 1,4-Diaminoanthrachinon mit Mangandioxid in Schwefelsäure. Für die meisten Zwecke genügt es, (II) in technischer Qualität (etwa 95 gew.%iger Reinheit) einzusetzen.1-Amino-4-hydroxyanthraquinone (II) is known and can be obtained by known methods, e.g. by reacting 1,4-diaminoanthraquinone with manganese dioxide in sulfuric acid. For most purposes it is sufficient to use (II) in technical quality (about 95% by weight purity).
Die Ausgangsverbindung (II) wird in der inerten organischen Flüssigkeit suspendiert. Als inerte aprotische organische Flüssigkeiten eignen sich solche Verbindungen, die unter den Reaktionsbedingungen selber nur in unbedeutenden Mengen reagieren, darunter vorzugsweise mit elektronenziehenden Gruppen substituierte Monoaromaten wie beispielsweise Nitrobenzol, o-Dichlorbenzol, Trichlorbenzol oder Benzoesäuremethylester.The starting compound (II) is suspended in the inert organic liquid. Suitable inert aprotic organic liquids are those compounds which themselves react only in insignificant amounts under the reaction conditions, including, preferably, monoaromatics substituted with electron-withdrawing groups, such as, for example, nitrobenzene, o-dichlorobenzene, trichlorobenzene or methyl benzoate.
Die Menge an inerter organischer Flüssigkeit beträgt in der Regel 4 bis 12, vorzugsweise 6 bis 9 kg pro kg (II).The amount of inert organic liquid is generally 4 to 12, preferably 6 to 9 kg per kg (II).
Als Bromierungsmittel verwendet man Phosphortribromid, -oxybromid oder -pentabromid oder vor allem elementares Brom. Man setzt diese Verbindungen im allgemeinen in stöchiometrischen Mengen ein, jedoch kann es sich auch empfehlen, das Bromierungsmittel in einem Überschuß von 20 äqu.-% zu verwenden. Ein größerer Überschuß ist im Hinblick auf die Aufarbeitung des Reaktionsgemisches weniger ratsam.Phosphorus tribromide, oxybromide or pentabromide or, above all, elemental bromine are used as brominating agents. These compounds are generally used in stoichiometric amounts, but it may also be advisable to use the brominating agent in an excess of 20 eq.%. A larger excess is less advisable with regard to working up the reaction mixture.
Im allgemeinen führt man die Reaktion bei 100 bis 180, vorzugsweise bei 120 bis 140°C durch.In general, the reaction is carried out at 100 to 180, preferably at 120 to 140 ° C.
Verfahrenstechnisch geht man im allgemeinen so vor, daß man eine Suspension von II in der organischen Phase vorlegt und das Bromierungsmittel bei der Reaktionstemperatur zugibt. Gegebenenfalls kann man die Temperatur im Laufe der fortschreitenden Reaktion noch erhöhen.In terms of process engineering, the procedure is generally such that a suspension of II in the organic phase is initially introduced and the brominating agent is added at the reaction temperature. If necessary, the temperature can be increased as the reaction progresses.
Zweckmäßigerweise führt man die Reaktion bei Normaldruck durch, aber es ist ach möglich, in einem geschlossenen System unter Eigendruck zu arbeiten.The reaction is expediently carried out under normal pressure, but it is also possible to work in a closed system under autogenous pressure.
Man kann die Umsetzung nach den üblichen Techniken auch kontinuierlich, z.B. in einer Rührkesselkaskade, vornehmen.The implementation can also be carried out continuously using the usual techniques, e.g. in a cascade of stirred tanks.
Der Reaktionsverlauf wird zweckmäßigerweise dünnschichtchromatographisch überwacht. Wenn die Ausgangsverbindung (11) nur noch in Spuren vorhanden ist, kühlt man das Reaktionsgemisch zweckmäßigerweise auf ca. 25°C ab, wonach man wie üblich auf das Verfahrensprodukt aufarbeitet, z.B. indem man es mit Methanol aus der organischen Lösung ausfällt. Der ausfallende Feststoff wird abfiltriert und mit Methanol und Wasser gewaschen. Er enthält in der Regel 90 bis 98 Gew.% (I). Die Reinheit kann nach den üblichen Techniken chromatographisch-photometrisch bestimmt werden.The course of the reaction is expediently monitored by thin layer chromatography. If the starting compound (11) is only present in traces, the reaction mixture is expediently cooled to about 25 ° C., after which the product is worked up in the customary manner, for example by it precipitates from the organic solution with methanol. The precipitated solid is filtered off and washed with methanol and water. It usually contains 90 to 98 wt.% (I). The purity can be determined chromatographically-photometrically using the usual techniques.
1-amino-2-brom-4-hydroxy-anthrachinon (II) ist ein wichtiges Zwischenprodukt bei der Herstellung von Anthrachinonfeststoffen, wie z.B. Disperse Red 60 und Disperse Red 91.1-amino-2-bromo-4-hydroxy-anthraquinone (II) is an important intermediate in the production of anthraquinone solids such as e.g. Disperse Red 60 and Disperse Red 91.
Das erfindungsgemäße Verfahren liefert (I) in hervorragender Reinheit und Ausbeute.The process according to the invention gives (I) in excellent purity and yield.
30 g 1-Amino-4-hydroxy-anthrachinon (95 gew.-%ig) wurden in 250 g Nitrobenzol suspendiert und auf 100°C erwärmt. Nachdem 22 g Brom innerhalb von 15 min zugetropft worden waren, wurde die Temperatur des Reaktionsgemisches während einer Zeitspanne von einer Stunde auf 130 bis 140°C erhöht. Diese Temperatur wurde noch drei Stunden lang gehalten, und dann wurde das Reaktionsgemisch auf 25°C abgekühlt und mit 150 g Methanol versetzt. Das ausgefallene Reaktionsprodukt wurde abfiltriert, mit 150 g Methanol und dann mit Wasser gewaschen und anschließend getrocknet.30 g of 1-amino-4-hydroxyanthraquinone (95% by weight) were suspended in 250 g of nitrobenzene and heated to 100.degree. After 22 g of bromine had been added dropwise within 15 minutes, the temperature of the reaction mixture was raised to 130 to 140 ° C. over a period of one hour. This temperature was maintained for a further three hours, and then the reaction mixture was cooled to 25 ° C. and 150 g of methanol were added. The precipitated reaction product was filtered off, washed with 150 g of methanol and then with water and then dried.
Man erhielt 38,6 g Produkt mit einem Gehalt an (I) von 97,1 %, was einer Ausbeute von 98,9 % entspricht.38.6 g of product with a (I) content of 97.1% were obtained, which corresponds to a yield of 98.9%.
30 g 1-Amino-4-hydroxy-anthrachinon (95 gew.%ig) wurden in 250 g Benzoesäuremethylester suspendiert und auf 110 bis 120°C erwärmt. Zu dieser Suspension wurden innerhalb von 15 min 22 g Brom getropft.30 g of 1-amino-4-hydroxyanthraquinone (95% by weight) were suspended in 250 g of methyl benzoate and heated to 110 to 120 ° C. 22 g of bromine were added dropwise to this suspension within 15 minutes.
Anschließend wurde das Reaktionsgemisch auf 130 bis 140°C erwärmt und 3 Stunden lang bei dieser Temperatur gehalten. Danach wurde auf 25°C abgekühlt und mit 250 g Methanol versetzt. Das ausgefallene Reaktionsprodukt wurde abfiltriert, zunächst mit 250 g Methanol, dann mit Wasser gewaschen und getrocknet.The reaction mixture was then heated to 130 to 140 ° C. and held at this temperature for 3 hours. The mixture was then cooled to 25 ° C. and 250 g of methanol were added. The precipitated reaction product was filtered off, washed first with 250 g of methanol, then with water and dried.
Man erhielt 36,9 g Produkt mit einem Gehalt an (I) von 98,2 %, was einer Ausbeute von 95,5 % entspricht.36.9 g of product with a (I) content of 98.2% were obtained, which corresponds to a yield of 95.5%.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3841988 | 1988-12-14 | ||
| DE3841988A DE3841988A1 (en) | 1988-12-14 | 1988-12-14 | METHOD FOR PRODUCING 1-AMINO-2-BROM-4-HYDROXY-ANTHRACHINONE |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0375990A2 true EP0375990A2 (en) | 1990-07-04 |
| EP0375990A3 EP0375990A3 (en) | 1991-02-27 |
| EP0375990B1 EP0375990B1 (en) | 1994-04-06 |
Family
ID=6369086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP89122183A Expired - Lifetime EP0375990B1 (en) | 1988-12-14 | 1989-12-01 | Process for the preparation of 1-amino-2-bromo-4-hydroxy-anthraquinone |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5082957A (en) |
| EP (1) | EP0375990B1 (en) |
| JP (1) | JPH02204473A (en) |
| DE (2) | DE3841988A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0649833A1 (en) * | 1993-10-21 | 1995-04-26 | BASF Aktiengesellschaft | Process for the preparation of anthraquinonamine compounds |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456616B (en) * | 2022-03-01 | 2024-03-15 | 常州大学 | Synthesis method of disperse red 60 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3086977A (en) * | 1960-01-12 | 1963-04-23 | Gen Aniline & Film Corp | Basic anthraquinone dyestuffs |
| FR1352537A (en) * | 1963-04-01 | 1964-02-14 | Acna | Process for the production of a blue dye, dye thus obtained and applications |
| JPS5018526A (en) * | 1973-06-19 | 1975-02-27 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1239778A (en) * | 1968-10-03 | 1971-07-21 | Ici Ltd | Halogenation process |
| DE2713575C2 (en) * | 1977-03-28 | 1979-06-07 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of 1-amino-2-bromo-4-hydroxyanthraquinone |
| JPS5642631A (en) * | 1979-09-14 | 1981-04-20 | Matsushita Electric Works Ltd | Manufacture of foamed decorative lamination sheet for building |
| US4648994A (en) * | 1985-02-04 | 1987-03-10 | Ciba-Geigy Corporation | Process for the preparation of 1-amino-2-bromo-4-hydroxyanthraquinone |
| EP0250362B1 (en) * | 1986-06-16 | 1992-01-02 | Ciba-Geigy Ag | Process for the preparation of a mixture of 1-amino-2-chloro-4-hydroxy-anthraquinone and 1-amino-2-bromo-4-hydroxy-anthraquinone |
-
1988
- 1988-12-14 DE DE3841988A patent/DE3841988A1/en not_active Withdrawn
-
1989
- 1989-11-17 US US07/437,660 patent/US5082957A/en not_active Expired - Fee Related
- 1989-12-01 DE DE89122183T patent/DE58907407D1/en not_active Expired - Lifetime
- 1989-12-01 EP EP89122183A patent/EP0375990B1/en not_active Expired - Lifetime
- 1989-12-08 JP JP1317924A patent/JPH02204473A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3086977A (en) * | 1960-01-12 | 1963-04-23 | Gen Aniline & Film Corp | Basic anthraquinone dyestuffs |
| FR1352537A (en) * | 1963-04-01 | 1964-02-14 | Acna | Process for the production of a blue dye, dye thus obtained and applications |
| JPS5018526A (en) * | 1973-06-19 | 1975-02-27 |
Non-Patent Citations (1)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 83, 1975, Seite 123, Zusammenfassung Nr. 81233s, Columbus, Ohio, US; & JP-A-50 018 526 (NIPPON KAYAKU CO., LTD) 27-02-1975 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0649833A1 (en) * | 1993-10-21 | 1995-04-26 | BASF Aktiengesellschaft | Process for the preparation of anthraquinonamine compounds |
| US5525743A (en) * | 1993-10-21 | 1996-06-11 | Basf Aktiengesellschaft | Preparation of anthraquinone imide compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0375990A3 (en) | 1991-02-27 |
| DE3841988A1 (en) | 1990-06-21 |
| JPH02204473A (en) | 1990-08-14 |
| EP0375990B1 (en) | 1994-04-06 |
| DE58907407D1 (en) | 1994-05-11 |
| US5082957A (en) | 1992-01-21 |
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